A Quantum-Guided Molecular Mechanics Force Field for the Ferrocene Scaffold
A Quantum-Guided Molecular Mechanics Force Field for the Ferrocene Scaffold
复制标题
二茂铁支架的量子引导分子力学力场
DOI：
10.1021/acs.joc.2c01553
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Wiest, Olaf
中科院分区：
文献类型：
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作者：
Wahlers, Jessica;Rosales, Anthony R.;Berkel, Neil;Forbes, Aaron;Helquist, Paul;Norrby, Per-Ola;Wiest, Olaf
二茂铁衍生物具有广泛的应用，包括作为不对称催化中的配体，因为它们具有化学稳定性、刚性主链、空间体积以及通过平面手性编码立体化学信息的能力。不幸的是，很少有可用的分子力学力场包含用于精确研究这一重要组成部分的参数。在这里，我们提出了二茂铁基配体的 MM3* 力场，该力场是使用量子引导分子力学 (Q2MM) 方法生成的。通过与 DFT 计算和晶体结构进行比较进行详细验证，证明了参数的准确性，并通过过剩能量分析揭示了偏差的物理根源。将二茂铁力场与 Pd-烯丙基配合物的力场相结合并比较晶体结构，表明与先前开发的 MM3* 力场的兼容性。最后，将二茂铁力场与之前发表的过渡态力场相结合，预测了不同胺和不同手性二茂铁基配体的 Pd-烯丙基配合物的胺化立体化学结果，在 10 个例子中，R2 约为 0.91。
Ferrocene derivatives have a wide range of applications, including as ligands in asymmetric catalysis, due to their chemical stability, rigid backbone, steric bulk, and ability to encode stereochemical information via planar chirality. Unfortunately, few of the available molecular mechanics force fields incorporate parameters for the accurate study of this important building block. Here, we present a MM3* force field for ferrocenyl ligands, which was generated using the quantum-guided molecular mechanics (Q2MM) method. Detailed validation by comparison to DFT calculations and crystal structures demonstrates the accuracy of the parameters and uncovers the physical origin of deviations through excess energy analysis. Combining the ferrocene force field with a force field for Pd–allyl complexes and comparing the crystal structures shows the compatibility with previously developed MM3* force fields. Finally, the ferrocene force field was combined with a previously published transition-state force field to predict the stereochemical outcomes of the aminations of Pd–allyl complexes with different amines and different chiral ferrocenyl ligands, with anR2of ∼0.91 over 10 examples.